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| United States Patent |
5,539,060
|
|
Tsunogae
, et al.
|
July 23, 1996
|
Method for hydrogenation of metathesis polymers
Abstract
The present invention provides a method for hydrogenating a metathesis
polymer solution obtained by polymerization in the presence of a
metathesis polymerization catalyst comprising (a) the catalyst component
of a transition metal compound and (b) the co-catalyst component of a
metal compound by bringing the above solution into contact with hydrogen,
without adding an inactivating agent for the metathesis polymerization
catalyst, that is, with the solution left to contain the catalyst, in the
presence of a hydrogenation catalyst comprising a transition metal
compound (c) and a reductive metal compound (d) and if necessary by adding
an acid-binding compound. According to this method, both addition of the
inactivating agent and removal of the metathesis polymerization catalyst
are not necessary, and also the hydrogenation can be carried out at a
lower temperature and under a lower pressure than in hydrogenation with a
supported-type catalyst, so that the efficiency of production of the
hydrogenated product is excellent. Besides, even if tungsten hexachloride
(WCl.sub.6), etc. are used as the catalyst component, an effect of
preventing a hydrogenation reactor from corrosion by a hydrogen halide,
can be obtained.
| Inventors:
|
Tsunogae; Yasuo (Kawasaki, JP);
Mizuno; Hideharu (Kawasaki, JP);
Kohara; Teiji (Kawasaki, JP);
Natsuume; Tadao (Yokosuka, JP)
|
| Assignee:
|
Nippon Zeon Co., Ltd. (Tokyo, JP)
|
| Appl. No.:
|
542654 |
| Filed:
|
October 13, 1995 |
Foreign Application Priority Data
| Jul 30, 1993[JP] | 5-208509 |
| Sep 30, 1993[JP] | 5-269619 |
| Current U.S. Class: |
525/338; 525/326.1; 525/328.1; 525/331.7; 525/332.8; 525/333.1; 525/333.2; 525/333.4 |
| Intern'l Class: |
C08F 008/04 |
| Field of Search: |
525/338,339
|
References Cited
U.S. Patent Documents
| 5106920 | Apr., 1992 | Murakami et al. | 525/326.
|
| 5164469 | Nov., 1992 | Goto et al. | 525/338.
|
Primary Examiner: Lipman; Bernard
Attorney, Agent or Firm: Armstrong, Westerman, Hattori, McLeland & Naughton
Parent Case Text
This application is a continuation of application Ser. No. 08/282,596 filed
Jul. 29, 1994, now abandoned.
Claims
What is claimed is:
1. A method for preparing a hydrogenated metathesis polymer which
comprises:
metathetically polymerizing a monomer in the presence of a metathesis
catalyst comprising (a) a catalyst component of a transition metal
compound and (b) a co-catalyst component of a metal compound, and, without
inactivating the metathesis catalyst,
hydrogenating the thus formed metathesis polymer in the presence of a
hydrogenation catalyst comprising (c) a transition metal compound and (d)
a reductive metal compound.
2. A method for preparing a hydrogenated metathesis polymer which
comprises:
metathetically polymerizing a monomer in a reaction system containing a
metathesis catalyst comprising (a) a catalyst component of a transition
metal compound and (b) a co-catalyst component of a metal compound, and,
without inactivating the metathesis catalyst,
hydrogenating the thus formed metathesis polymer in the presence of a
hydrogenation catalyst comprising (c) a transition metal compound and (d)
a reductive metal compound,
adding an acid-binding compound to the reaction system,
and recovering the hydrogenated metathesis polymer from the reaction
system.
3. A method according to claim 1, wherein the transition metal compound (c)
is the organometal compound, halide, alkoxide, acetylacetonate, sulfonate
or naphthenate of V, ti, Mn, Fe, Co or Ni.
4. A method according to claim 3, wherein the transition metal compound (c)
is the organometal compound, alkoxide or acetylacetonate of Ti, Fe, Co or
Ni.
5. A method according to claim 1, wherein the reductive metal compound (d)
is the organometal compound or hydride of Al, Li, Zn or Mg.
6. A method according to claim 5, wherein the reductive metal compound (d)
is alkylaluminum or alkyllithium.
7. A method according to claim 1, wherein the catalyst component of a
transition metal compound (a) is the halide, oxyhalide or alkoxyhalide of
W, Mo, ti or V.
8. A method according to claim 7, wherein the co-catalyst component of a
metal compound (b) is the organic compound of Al, Sn, Li, Na, Mg, Zn, Cd
or B.
9. A method according to claim 1, wherein the monomer is a monocyclic
cycloolefin, polycyclic cycloolefin, acetylenes or dienes having double
bonds at the both ends.
10. A method according to claim 1, wherein metathesis polymerization of the
monomer is carried out in an inert organic solvent.
11. A method according to claim 10, wherein the inert organic solvent is an
aromatic hydrocarbon, alicyclic hydrocarbon, halogenated hydrocarbon
and/or an ether.
12. A method according to claim 10, wherein the amount of the inert organic
solvent is 1 to 100 times by weight that of the monomer.
13. A method according to claim 1, wherein the amount of the catalyst
component of a transition metal compound (a) is 0.000001 to 1 time by mole
that of the monomer.
14. A method according to claim 1, wherein the amount of the co-catalyst
component of a metal compound (b) is 1 to 100 times that of the catalyst
component of a transition metal compound (a) in terms of the molar ratio
of the metal atoms contained in the components (b) and (a).
15. A method according to claim 1, wherein the amount of the transition
metal compound (c) is 0.001 to 1000 mmoles based on 100 g of the
metathesis polymer.
16. A method according to claim 1, wherein the amount of the reductive
metal compound (d) is 0.5 to 50 times that of the transition metal
compound (c) in terms of the molar ratio of the metal atoms contained in
the compounds (d) and (c).
17. A method according to claim 1, wherein the hydrogenation rate of the
unsaturated bond contained in the main chain structure of the metathesis
polymer is 50% or more.
18. A method according to claim 2, wherein the acid-binding compound is an
epoxy compound.
19. A method according to claim 18, wherein the acid-binding compound is
ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide,
styrene oxide, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl
ether, phenyl glycidyl ether, ethylene glycol diglycidyl ether or an epoxy
resin.
Description
FIELD OF THE INVENTION AND RELATED ART STATEMENT
1. Field of the Invention
The present invention relates to a method for hydrogenation of metathesis
polymers. More particularly, it relates to a method for hydrogenation of
metathesis polymers in which the unsaturated bonds in the main chain of
the polymers are saturated with a good efficiency and under mild
conditions.
2. Related Art
The metathesis polymer is widely produced in industry. Since, however, it
contains unsaturated bonds in the structure of the main chain, there are
problems in terms of weather resistance, oxidation resistance, heat
resistance and the like. In order to dissolve these problems, it is widely
carried out to saturate the structure of the main chain by hydrogenation
of the polymer.
In the hydrogenation step after metathesis polymerization of the monomer,
in order to prevent the hydrogenation catalyst from activity reduction
caused by impurities, it is a common practice to extract and remove the
metathesis polymerization catalyst by adding an inactivating agent for
this catalyst to the solution in which the hydrogenation is to be carried
out (Japanese Patent Application Kokai No. 1-311120). However, it is also
known a method of obtaining the hydrogenated product of the metathesis
polymer by directly adding the hydrogenation catalyst without removing the
metathesis polymerization catalyst from the metathesis polymerization
solution and then contacting the solution with hydrogen (as disclosed, for
example, in Japanese Patent Application Kokai No. 1-138257, No. 1-311120,
No. 2-286712, No. 4-93321, etc.). Of such the hydrogenation methods, only
one specific example in which a highly active supported-type catalyst is
used as the hydrogenation catalyst, is known (Japanese Patent Application
Kokai No. 2-286712).
The supported-type hydrogenation catalyst is superior in production
efficiency in that it is so highly active that hydrogenation is attained
in a short time, and also that this catalyst is easily removable. This
catalyst is therefore widely used. However, both high temperature and high
pressure are necessary to carry out this hydrogenation. And besides, since
this catalyst is a lump in which the catalyst component has been supported
on the carrier, its sufficient dispersion in the polymer solution is
difficult, and therefore this catalyst needs to be added in large amounts.
Because of this, there is a problem of costing too much in industrial
production. Further, both high temperature and high pressure are
necessary, so that decomposition and gelation of the polymer are easy to
occur, which sometimes causes a problem of the quality of polymer.
For removing the metathesis polymerization catalyst, there are a method of
removing the catalyst by washing the polymerization solution with a
solution containing an inactivating agent for this catalyst, and a method
of removing the catalyst by changing the catalyst into a solid catalyst
residue and then removing this residue by filtration or centrifugation. In
these methods, however, it is difficult to completely remove the catalyst
residue, and it often occurs that the catalyst residue enters the
hydrogenation step. In such a case, it is sometimes observed that the
catalyst residue hydrolyzes at the hydrogenation step to generate a
hydrogen halide, which corrodes the reaction vessel.
Also, in the method in which the polymerization solution is directly
supplied to the hydrogenation step without removing the polymerization
catalyst itself or its residue, the production process is simplified, so
that there is an advantage of the production efficiency being excellent.
However, the polymerization catalyst or its residue is contained in the
production process, so that there is a problem that a hydrogen halide is
generated in large amounts and the corrosion of the equipment is
remarkable.
The catalyst used in the hydrogenation includes the foregoing
supported-type catalyst and a catalyst in which a transition metal
compound (c) and a reductive metal compound (d) have been combined with
each other. The latter catalyst is easily dispersible in the polymer
solution, so that addition of small amounts of it will suffice, and also
both high temperature and high pressure are not necessary. This catalyst,
therefore, is superior to the supported-type catalyst in that the cost is
low and the quality of the polymer is stable. The activity of this
catalyst varies with combination of the transition metal compound (c) and
reductive metal compound (d). In hydrogenation of the metathesis polymer,
however, the highly active supported-type catalyst is present, so that the
combination giving a high activity is not sufficiently investigated about
the combined catalyst. The known combined catalyst is normally low in the
activity as compared with the supported-type catalyst, and has problems
that it takes much time to complete the hydrogenation, and the effects of
impurities on hindrance to the reaction and reduction of the activity are
large. Because of this, even if a method itself is known, as described
above, in which hydrogenation is carried out without isolating the polymer
from the metathesis polymerization solution, nothing concrete is known
about a method of using the catalyst in which the transition metal
compound (c) and reductive metal compound (d) have been combined with each
other. Therefore, it has been considered that the metathesis polymer
cannot be hydrogenated with a good efficiency in the presence of the
metathesis polymerization catalyst whether the catalyst has been
inactivated or not.
SUMMARY OF THE INVENTION
The present inventors have made an extensive study on a method for
hydrogenating the metathesis polymer with excellent production efficiency,
and as a result have found that even if the metathesis polymer contains
the non-inactivated metathesis polymerization catalyst comprising (a) the
catalyst component of a transition metal compound and (b) the co-catalyst
component of a metal compound, the metathesis polymer can be hydrogenated
with a good efficiency using the combined catalyst of the transition metal
compound (c) with the reductive metal compound (d), particularly, using
the combined catalyst having high activity, and on the other hand, that
the activity of the combined catalyst of the transition metal compound (c)
with the reductive metal compound (d) reduces when the inactivating agent
for the metathesis polymerization catalyst is added. The present inventors
thus completed the present invention.
Further, the present inventors have made an extensive study with the object
of developing a method for hydrogenating the ring-opened polymer of a
cyclo-olefin monomer which generates no hydrogen halide even if the
halogen compound of the transition metal is used in the metathesis
polymerization catalyst. As a result, they have found that generation of a
hydrogen halide can be inhibited by allowing an acid-binding compound to
exist at the time of hydrogenation. The present inventors thus completed
the present invention.
DETAILED DESCRIPTION OF THE INVENTION
According to the present invention, there is provided a method for
hydrogenation of a metathesis polymer characterized in that a metathesis
polymer solution obtained by polymerization in the presence of a
metathesis polymerization catalyst comprising (a) the catalyst component
of a transition metal compound and (b) the co-catalyst component of a
metal compound is brought into contact with hydrogen in the presence of a
hydrogenation catalyst comprising a transition metal compound (c) and a
reductive metal compound (d) without substantially inactivating the
metathesis polymerization catalyst.
Further, according to the present invention, there is provided a method for
producing the hydrogenated product of a cycloolefin ring-opened polymer by
bringing a polymer solution, which is obtained by ring-opening
polymerization of a cycloolefin monomer using a metathesis polymerization
catalyst comprising the halide of a transition metal and an organometal
compound, into contact with hydrogen in the presence of a hydrogenation
catalyst, said method being characterized in that an acid-binding compound
is allowed to exist in the hydrogenation system together with the
hydrogenation catalyst.
Monomer:
In the present invention, the monomer used to produce the metathesis
polymer includes, for example, monocyclic cycloolefins such as
cyclobutene, 1-methylcyclobutene, 3-methylcyclobutene,
3,4-diisopropenylcyclobutene, cyclopentene, 3-methylcyclopentene,
5,6-dihydrocyclopentadiene, cyclohexene, 4-ethylcyclohexene, cyclooctene,
1-methylcyclooctene, 5-methylcyclooctene, cyclooctatetraene,
1,5-cyclooctadiene, cyclododecene, etc.; polycyclic cycloolefins such as
bicyclo[3.2.0]-heptene, bicyclo[4.2.01octene, tetrahydroindene,
norbornene, norbornadiene, etc.; acetylenes such as acetylene and
substituted acetylenes (e.g. propyne, 1-butyne); and dienes having double
bonds at the both ends such as 1,6-heptadiene, etc.
Specific examples of the cycloolefin monomer used in the present invention
include, for example, the following:
1. The above norbornene, the alkyl-, alkylidene-or aromatic
group-substituted derivatives of the norbornene and the halogen- or polar
group-substituted products of these substituted or non-substituted
norbornene monomers (the polar group includes ester, alkoxy, cyano, amide,
imide, silyl, etc.). These compounds include, for example, 2-norbornene,
5-methyl-2-norbornene, 5,5-dimethyl-2-norbornene, 5-ethyl-2-norbornene,
5-butyl-2-norbornene, 5-ethylidene-2-norbornene,
5-methoxycarbonyl-2-norbornene, 5-cyano-2-norbornene,
5-methyl-5-methoxycarbonyl-2-norbornene, 5-phenyl-2-norbornene,
5,6-diethoxycarbonyl-2-norbornene,
1,4-methano-1,4,4a,9a-tetrahydro-9H-fluorene, etc.
2. Monomers in which one or more cyclopentadienes have added to norbornene,
and the same derivatives and substituted products as above obtained from
the monomers. These compounds include, for example,
1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene,
6-methyl-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene,
6-ethyl-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene,
6-ethylidene-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene,
6,6-dimethyl-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene,
6-methyl-6-methoxycarbonyl-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydrona
phthalene,
4,9:5,8-dimethano-2,3,3a,4,4a,5,8,8a,9,9a-decahydro-1H-benzoindene, etc.
3. Monomers having a polycyclic structure which are the multimer of
cyclopentadiene, and the same derivatives and substituted products as
above obtained from the monomers. These compounds include, for example,
dicyclopentadiene, 2,3-dihydrodicyclopentadiene,
4,9:5,8-dimethano-3a,4,4a,5,8,8a,9,9a-octahydro-1H-benzoindene, etc.
4. Addition products of cyclopentadiene with tetrahydroindene, etc., and
the same derivatives and substituted products as above obtained from the
addition products. These compounds include, for example,
1,4-methano-1,4,4a,4b,5,8,8a,9a-octahydro-9H-fluorene,
5,8-methano-3a,4,4a,5,8,8a,9,9a-octahydro-1H-benzoindene,
1,4:5,8-dimethano-1,2,3,4,4a,4b,7,8,8a,9a-decahydro-9H-fluorene,
1,4-methano-1,4,4a,9a-tetrahydrofluorene, etc.
These monomers may be used alone or in combination of two or more of them.
For the purpose of regulation of the molecular weight, etc., acyclic
olefins, preferably .alpha.-olefins (e.g. ethylene, propylene, 1-butene,
isobutene, styrene, 1-hexene, 4-methylpentene, etc.) may be used as a
comonomer in an amount, usually, up to 10 mole%.
Metathesis polymerization catalyst:
The metathesis polymerization catalyst used in the present invention is
known, for example, as disclosed in Japanese Patent Application Kokoku No.
41-20111, Japanese Patent Application Kokai No. 46-14910, Japanese Patent
Application Kokoku No. 57-17883 and No. 57-61044, and Japanese Patent
Application Kokai No. 54-86600, No. 58-127728 and No. 1-240517. Usually,
this catalyst consists substantially of (a) the catalyst component of a
transition metal compound and (b) the co-catalyst component of a metal
compound.
The catalyst component of a transition metal compound (a) used in the
metathesis polymerization catalyst is the compound of transition metals
belonging to Groups IVB, VB, VIB, VIIB or VIII of Deming's periodic table.
This compound includes the halide, oxyhalide, alkoxyhalide, alkoxide,
carboxylate, (oxy)acetylacetonate, carbonyl complex, acetonitrile complex,
hydride complex of these transition metals, their derivatives, and
complexes of these compounds or their derivatives with a complexing agent
such as P(C.sub.6 H.sub.5).sub.5, etc.
Specific examples include TiCl.sub.4, TiBr.sub.4, VOCl.sub.3, VOBr.sub.3,
WBr.sub.4, WBr.sub.6, WCl.sub.2, WCl.sub.4, WCl.sub.5, WCl.sub.6,
WF.sub.4, WI.sub.2, WOBr.sub.4, WOCl.sub.4, WOF.sub.4, MoBr.sub.2,
MoBr.sub.3, MoBr.sub.4, MoCl.sub.4, MoCl.sub.5, MoF.sub.4, MoOCl.sub.4,
MoOF.sub.4, WO.sub.2, H.sub.2 WO.sub.4, NaWO.sub.4, K.sub.2 WO.sub.4,
(NH.sub.4).sub.2 WO.sub.4, CaWO.sub.4, CuWO.sub.4, MgWO.sub.4, (CO).sub.5
WC (OCH.sub.3)(CH.sub.3), (CO).sub.5 WC (OC.sub.2 H.sub.5)(CH.sub.3),
(CO).sub.5 WC(OC.sub.2 H.sub.5)(C.sub.4 H.sub.5), (CO).sub.5 MoC (OC.sub.2
H.sub.5)(CH.sub.3), (CO).sub.5 Mo=C (C.sub.2 H.sub.5), (N(C.sub.2
H.sub.5).sub.2), tridecylammonium molybdate, tridecylammonium tungstate,
etc. Practically, the compound of W, Mo, Ti or V, particularly the halide,
oxyhalide or alkoxyhalide of these metals is preferred in terms of
polymerization activity.
The co-catalyst component of a metal compound (b) used in the metathesis
polymerization catalyst is the compound of metals belonging to Groups, IA,
IIA, IIB, IIIA or IVA of Deming's periodic table, which compound needs to
have at least one metal element-carbon bond or metal element-hydrogen
bond. Such the compound includes, for example, the organic compound of Al,
Sn, Li, Na, Mg, Zn, Cd, B, etc. Specifically, there are given
organoaluminum compounds such as trimethylaluminum, triethylaluminum,
tri-n-propylaluminum, triisopropylaluminum, triisobutylaluminum,
trihexylaluminum, trioctylaluminum, triphenylaluminum, tribenzylaluminum,
diethylaluminum monochloride, di-n-propylaluminum monochloride,
diisobutylaluminum monochloride, di-n-butylaluminum monochloride,
diethylaluminum monobromide, diethylaluminum monoiodide, diethylaluminum
monohydride, di-n-propylaluminum monohydride, diisobutylaluminum
monohydride, methylaluminum sesquichloride, ethylaluminum sesquibromide,
isobutylaluminum sesquibromide, ethylaluminum dichloride, ethylaluminum
dibromide, propylaluminum dichloride, isobutylaluminum dichloride,
ethylaluminum dibromide, ethylaluminum diiodide, etc.; organotin compounds
such as tetramethyltin, diethyldimethyltin, tetraethyltin,
dibutyldiethyltin, tetrabutyltin, tetraisocumyltin, tetraphenyltin,
triethyltin fluoride, triethyltin chloride, triethyltin bromide,
triethyltin iodide, diethyltin difluoride, diethyltin diiodide, ethyltin
trifluoride, ethyltin trichloride, ethyltin tribromide, ethyltin
triiodide, etc.; organolithium compounds such as n-butyllithium, etc.;
organosodium compounds such as n-pentylsodium, etc.; organomagnesium
compounds such as methylmagnesium iodide, ethylmagnesium bromide,
methylmagnesium bromide, n-propylmagnesium chloride, tert-butylmagnesium
chloride, allylmagnesium chloride, etc.; organozinc compounds such as
diethylzinc, etc.; organocadmium compounds such as diethylcadmium, etc.;
organoboron compounds such as trimethylboron, triethylboron,
tri-n-butylboron, etc.; and the like.
The metathesis polymerization activity can be enhanced by adding a third
component besides the components (a) and (b). Such the third component
includes aliphatic tertiary amines, aromatic tertiary amines,
molecule-form oxygen, alcohols, ethers, peroxides, carboxylic acids, acid
anhydrides, acid chlorides, esters, ketones, nitrogen-containing
compounds, sulfur-containing compounds, halogen-containing compounds,
molecule-form iodine, other Lewis acids and the like. Of these compounds,
aliphatic or aromatic tertiary amines are preferred. Specific examples of
these amines include triethylamine, dimethylaniline, tri-n-butylamine,
pyridine, .alpha.-picoline and the like. Also, when compounds having an OH
group such as alcohols, etc. are added in amounts exceeding their
stoichiometric amount, they function as an inactivating agent disturbing
the metathesis polymerization activity. The alcohols, therefore, need to
be added in amounts not exceeding their stoichiometric amount. The
stoichiometric amount referred to herein means a mole number represented
by a numerical value obtained by dividing the product of mole number of
the component (a) and oxidation number of the transition metal contained
in the component (a) by the number of OH groups per one molecule of the OH
group-containing compound.
As to the relation between the amounts of these components, the ratio of
amounts of the components (a) and (b) is 1:1 to 1:100, preferably 1:2 to
1:50 in terms of the molar ratio of the metal elements contained in the
components, and that of amounts of the component (a) and third component
is usually 1:0.005 to 1:10, preferably 1:0.05 to 1:3 in terms of the molar
ratio of the both components. When the amount of the component (b) is too
small relative to that of the component (a), a sufficient activity
expectable from the amount of the component (a) can not be obtained. When
the amount of the component (b) is too large, removal of the excess
component (b) becomes difficult, which raises the cost. When the amount of
the third component is too small relative to that of the component (a),
the effect of addition of the third component is small, and when the
amount of the third component is too large, removal of the excess third
component becomes difficult, which raises the cost.
Metathesis polymerization:
In the present invention, metathesis polymerization can be carried out
without a solvent, but it can be carried out even in an inert organic
solvent. For example, polymerization of the norbornene monomer is
generally carried out in an inert organic solvent. Specific examples of
such the solvent include aromatic hydrocarbons such as benzene, toluene,
xylene, etc.; alicyclic hydrocarbons such as cyclohexane, etc.;
halogenated hydrocarbons such as methylene dichloride, dichloroethane,
dichloroethylene, tetrachloroethane, chlorobenzene, dichlorobenzene,
trichlorobenzene, etc.; ethers such as diethyl ether, etc.; and the like.
These solvents may be used in mixture of two or more of them. The amount
of the solvent is in the range of usually 1 to 100 times, preferably 2 to
20 times in terms of a weight ratio to the amount of the monomer. When the
amount of the solvent is too small, the viscosity of the polymerization
solution becomes high with the progress of the polymerization, so that it
is difficult to obtain a polymer having a high polymerization degree. When
the amount of the solvent is too large, the catalyst and monomer become
difficult to contact with each other, so that the reaction rate becomes
slow and efficiency becomes bad.
The amount of the metathesis polymerization catalyst is in the range of
usually 0.000001 to 1 time, preferably 0.0001 to 0.5 time in terms of the
molar ratio of amount of the component (a) contained in the catalyst to
amount of the monomer. Whether the amount of the component (a) is too
small or too large, the monomer and catalyst become difficult to contact
with each other, so that the reaction rate becomes slow and efficiency
becomes bad.
The molecular weight of the resulting metathesis polymer can be regulated
by adding to the reaction solution a compound having at least C--C double
bond or C--C triple bond in the molecule or a polar allyl compound. The
former compound includes .alpha.-olefins, .alpha.,.omega.-diolefins,
acetylenes, etc., and the latter compound includes allyl chloride, allyl
acetate, trimethylallyloxysilane, etc.
The temperature condition for metathesis polymerization is not critical,
but it is usually -20.degree. C. to 100.degree. C., preferably 10.degree.
to 50.degree. C., more preferably 20.degree. C. to 50.degree. C. When the
temperature is too low, the reaction rate lowers, and when it is too high,
the reaction becomes difficult to control and energy cost becomes high.
The metathesis polymerization is carried out under a pressure of usually
0.1 to 50 kgf/cm.sup.2, preferably 0.5 to 10 kgf/cm.sup.2, more preferably
1 to 5 kgf/cm.sup.2.
Metathesis polymer:
The metathesis polymer used in the present invention may be any of a
homopolymer and copolymer, so far as it is a polymer produced with the
metathesis polymerization catalyst. And the copolymer may be any of a
random copolymer, block copolymer and graft copolymer. Also, the
metathesis polymer used in the present invention needs to have a weight
average molecular weight of usually 1,000 to 1,000,000, preferably 5,000
to 200,000 as measured by GPC. Metathesis polymer solution containing
metathesis polymerization catalyst:
In the present invention, the metathesis polymer solution obtained by
polymerization in the presence of the metathesis polymerization catalyst
is hydrogenated by contacting it with hydrogen in the presence of the
hydrogenation catalyst without inactivating the metathesis polymerization
catalyst before hydrogenation. Therefore, the inactivation step can be
omitted and production efficiency is good. When the metathesis polymer
solution is supplied to the hydrogenation step after a large amount of the
inactivating agent (e.g. a compound having an OH group such as water,
alcohols, etc.) is added according to the conventional method, the
activity of the hydrogenation catalyst largely lowers. Even if the
metathesis polymer is once isolated by coagulation, re-dissolved in the
solvent and then supplied to the hydrogenation step, the activity of the
hydrogenation catalyst is insufficient. However, if the metathesis
polymerization catalyst is not substantially inactivated and therefore the
unreacted inactivating agent is not present in the system, the activity of
the hydrogenation catalyst is sufficient.
The concentration of this polymer solution is preferably 1 to 50 wt. %,
more preferably 5 to 30 wt. %. When the concentration is too high, it may
be diluted to a desirable one by adding additional inert organic solvent.
Hydrogenation catalyst:
The hydrogenation catalyst used in the present invention comprises a
transition metal compound (c) and reductive metal compound (d). This
catalyst is known, for example, as disclosed in Japanese Patent
Application Kokai No. 58-43412, No. 60-26024, No. 64-24826 and No.
1-138257.
In the present invention, the transition metal compound (c) used in the
hydrogenation catalyst is the compound of transition metals belonging to
either of Groups I or IV to VIII of Deming's periodic table. Specifically,
there are given, for example, the compound of transition metals such as V,
Ti, Cr, Mo, Zr, Fe, Mn, Co, Ni, Pd, Ru, etc., and the compound includes
halides, alkoxides, acetylacetonates, sulfonates, carboxylates,
naphthenates, trifluoroacetates and stearates of these metals. Specific
examples of the compound include tetraisopropoxy titanate, tetrabutoxy
titanate, titanocene dichloride, zirconocene dichloride, vanadocene
dichloride, triethyl vanadate, tributyl vanadate, chromium(III)
acetylacetonate, molybdenyl acetylacetonate, manganese(III)
acetylacetonate, iron(III) acetylacetonate, cobalt(III) acetylacetonate,
bis(triphenylphosphine)cobalt dichloride, nickel(II) acetylacetonate,
bis(tributylphosphine)nickel dichloride, bis(tributylphosphine)palladium
dichloride, bis(cyclopentadienyl)titanium dichloride and the like.
In the present invention, the reductive metal compound (d) used in the
hydrogenation catalyst is specifically the compound of metals belonging to
Groups IA, IIA, IIB, IIIA or IVA of Deming's periodic table, which
compound needs to have at least one metal atom-carbon bond or metal
atom-hydrogen bond. Specifically, there are given aluminum compounds such
as trimethylaluminum, triethylaluminum, triisobutylaluminum,
triphenylaluminum, diethylaluminum chloride, ethylaluminum dichloride,
methylaluminum sesquichloride, ethylaluminum sesquichloride,
diethylaluminum hydride, diisobutylaluminum hydride, etc.; lithium
compounds such as methyllithium, ethyllithium, n-propyllithium,
n-butyllithium, sec-butyllithium, isobutyllithium, n-hexyllithium,
phenyllithium, p-tolyllithium, xylyllithium, etc.; zinc compounds such as
diethylzinc, bis(cyclopentadienyl)zinc, diphenylzinc, etc.; magnesium
compounds such as dimethylmagnesium, diethylmagnesium, methylmagnesium
bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium
chloride, phenylmagnesium bromide, phenylmagnesium chloride, etc.; and the
like. Compounds containing two or more kinds of reductive metal such as
lithiumaluminum hydride, etc. can also be used.
One of specific combined catalysts is those in which the component (c)
which is the organometal compound, halide, alkoxide, acetylacetonate,
sulfonate or naphthenate of V, Ti, Mn, Fe, Co or Ni, and the component (d)
which is the organic compound or hydride of Al, Li, Zn or Mg have been
combined with each other. These catalysts are preferred because they have
high activity and undergo only a little effect of impurities on hindrance
to the reaction and reduction of the activity. And, the other of specific
combined catalysts is those in which the component (c) which is the
organometal compound, halide, alkoxide or acetylacetonate of Ti, Fe, Co or
Ni, and the component (d) which is alkylaluminum or alkyllithium have been
combined with each other. These catalysts are more preferred because they
have particularly a high activity and undergo only particularly a little
effect of impurities on hindrance to the reaction and reduction of the
activity.
As to the relation between the amounts of these components, the amounts of
the components (c) and (d) is 1:0.5 to 1:50, preferably 1:1 to 1:8 in
terms of the molar ratio of metal atoms contained in the components.
Whether the amount of the component (d) is too large or too small relative
to that of the component (c), the hydrogenation activity becomes
insufficient. Particularly, when the amount is too large, gelation and
side reaction sometimes occur.
The unsaturated bond in the main chain structure of the polymer is
hydrogenated by these hydrogenation catalysts to turn saturated bond, but
usually, unsaturated bonds other than those in the main chain structure
are also hydrogenated and saturated. However, when the polymer contains an
aromatic ring, unsaturated bonds in this ring can be left unsaturated
without being hydrogenated, for example, by using a hydrogenation catalyst
in which bis(cyclopentadienyl)titanium dichloride which is the component
(c) and alkyllithium which is the component (d) have been combined with
each other (Japanese Patent Application Kokoku No. 63-4841), a
hydrogenation catalyst in which dialkyl-bis(cyclopentadienyl)titanium
which is the component (c) and a reductive magnesium compound which is the
component (d) have been combined with each other (Japanese Patent
Application Kokai No. 61-28507), or a hydrogenation catalyst in which
dialkyl-bis(cyclopentadienyl)titanium which is the component (c) and
alkoxylithiumwhich is the component (d) have been combined with each other
(Japanese Patent Application Kokai No. 1-275605).
Acid-binding compound:
When the catalyst component of a transition metal compound (a) constituting
the metathesis polymerization catalyst is a transition metal halide such
as TiCl.sub.4, WCl.sub.6, etc., or the transition metal compound (c)
constituting the hydrogenation catalyst is a transition metal halide such
as bis(tributylphosphine)nickel dichloride, etc., or the reductive metal
compound (d) is a metal halide such as ethylaluminum dichloride, etc., it
sometimes occurs that water is generated at the time of hydrogenation,
these metal halides are hydrolyzed by this water to evolve a hydrogen
halide and as a result the hydrogenation reactor is corroded.
In the present invention, it is desirable to inhibit corrosion of the
hydrogenation reactor, etc. by reacting the hydrogen halide with an
acid-binding compound.
The acid-binding compound is a compound reacting with a hydrogen halide,
and its specific examples include epoxy compounds such as ethylene oxide,
propylene oxide, butylene oxide, cyclohexene oxide, styrene oxide, methyl
glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, phenyl
glycidyl ether, ethylene glycol diglycidyl ether, epoxy resins, etc.;
basic compounds such as calcium hydroxide, magnesium hydroxide, calcium
oxide, magnesium oxide, etc.; powdery, granular or ribbon-formmetals such
as magnesium, aluminum, zinc, iron, etc.; and the like. Of these
acid-binding compounds, epoxy compounds are preferred in terms of their
high preventing effect on corrosion of the hydrogenation reactor.
The time at which the acid-binding compound is added may be any time before
and after addition of the hydrogenation catalyst, so far as it is a time
after finish of the polymerization and before beginning of the
hydrogenation.
When the acid-binding compound is used, its amount used is 0.5 equivalent
or more, preferably 1 to 100 equivalents, more preferably 2 to 10
equivalents based on the stoichiometric amount of an acid generated by
hydrolysis of the metathesis polymerization catalyst and hydrogenation
catalyst, in other words, the mole amount of the halogen atom contained in
the metathesis polymerization catalyst and hydrogenation catalyst. For
example, when the metathesis polymerization catalyst comprising WCl.sub.6
and triethylaluminum is used, a hydrogen halide is not generated from
triethylaluminum, but hydrogen chloride can be generated in amounts up to
a maximum of 6 moles based on 1 mole of WCl.sub.6. When the acid-binding
compound used is aluminum which turns trivalent metal ion, in order to
inhibit corrosion of the hydrogenation reactor by a hydrogen halide
generated from WCl.sub.6, the amount of the acid-binding compound used is
1 mole (=6 moles +3.times.0.5), preferably 2 to 200 moles, more preferably
4 to 20 moles based on 1 mole of WCl.sub.6. Similarly, the same proportion
of the acid-binding compound as above is used to prevent the reaction
reactor from corrosion by an acid generated by hydrolysis of the
hydrogenation catalyst.
When hydrogenation is carried out using the so-called homogeneous catalyst
in which the transition metal compound (c) and reductive metal compound
(d) have been combined with each other, as in the present invention, the
generated water reacts with the reductive metal compound (d), so that,
usually, the hydrogenation reactor, etc. are not corroded at the time of
hydrogenation. However, after the hydrogenation is finished, that is,
after the reaction solution in the reactor is contacted with oxygen in air
by the after-treatment of hydrogenation in which the hydrogenation is
stopped and the hydrogen gas in the reactor is replaced by air, the
reaction product of the reductive metal compound with water is oxidized
into water again to generate a hydrogen halide. It is preferred,
therefore, to add the acid-binding compound before finish of the
hydrogenation, that is, before contact of the reaction solution with air.
Hydorgenation:
The amount of the hydrogenation catalyst added to the metathesis polymer
solution containing the metathesis polymerization catalyst is usually
0,001 to 1000 mmoles, preferably 0.1 to 100 mmoles, in terms of the amount
of the transition metal compound, based on 100 g of the polymer. Addition
of excess catalyst costs high, and besides after-treatment such as
catalyst removal after hydrogenation is difficult.
The hydrogenation is carried out by introducing hydrogen into the polymer
solution, and for example, a method of sufficiently contacting the
introduced hydrogen with the polymer while stirring the solution, is
preferred. The hydrogen pressure used in the hydrogenation is usually 0.1
to 100 kg/cm.sup.2, preferably 2 to 40 kg/cm.sup.2. When the pressure is
too low, the hydrogenation does not proceed, and when it is too high, the
reaction becomes difficult to control, and also side reaction and gelation
are caused.
In the present invention, the hydrogenation is carried out at usually
0.degree. to 200.degree. C., preferably 20.degree. C. to 100.degree. C.
When the temperature is too low, the hydrogenation rate is slow, and when
it is too high, decomposition and gelation of the polymer are easy to
occur, and also energy cost becomes high.
The hydrogenation can be stopped by stopping supply of hydrogen. It may be
stopped by adding a compound having an OH group (e.g. water, alcohols) to
inactivate the hydrogenation catalyst.
Recovery and purification of hydrogenated product:
A method for recovering the hydrogenated product of the polymer from the
hydrogenation solution is not critical. For example, it will suffice to
coagulate the hydrogenated product of the polymer by adding a large amount
of a poor solvent (e.g. an alcohol) to the hydrogenation solution.
Hydrogenated product:
In the hydrogenated product obtained by the method of the present
invention, the unsaturated bond in the main chain structure of the polymer
has been saturated. The hydrogenation rate varies with the kind and amount
of the hydrogenation catalyst, hydrogenation temperature, hydrogen
pressure and the like. A desirable hydrogenation rate varies with the
object of hydrogenation. Generally, however, the rate of hydrogenation of
the unsaturated bond in the main chain structure is preferably 50% or
more, more preferably 90% or more, particularly preferably 99% or more.
Generally, when the rate of hydrogenation of the unsaturated bond in the
main chain structure is low, the heat resistance and light fastness become
poor.
Unsaturated bonds other than those in the main chain structure also are
generally hydrogenated at the same rate as in the main chain structure.
However, unsaturated bonds in an aromatic ring, as described before, can
be left unsaturated without being selectively hydrogenated by selecting
the hydrogenation catalyst. The hydrogenation rate of the unsaturated
bonds in the aromatic ring and that of other unsaturated bonds can be
measured in distinction from each other by infrared absorption spectrum.
The hydrogenated product of the metathesis polymer obtained by the present
invention is useful in a wide field as various kinds of molded article,
including optical materials. For example, there are given optical
materials (optical discs, optical lenses, prisms, light-diffusing plates,
optical cards, optical fibers, optical mirrors, substrates for liquid
crystal display elements, light-conducting plates, polarizing films, phase
retarder films, etc.), medical materials (e.g., containers for liquid,
powdery or solid medicines such as containers holding liquid medicines for
injection, ampoules, vials, pre-filled syringes, bags for transfusion,
sealed medicine bags, press through packages, containers for solid
medicines, containers for eye lotions, etc.; food containers; sampling
containers such as sampling test tubes for blood test, caps for medicine
containers, blood-collecting tubes, test sample containers, etc.,
sterilizing apparatus for medical tools such as injectors, surgical
knives, forceps, gauzes, contact lenses, etc.; experimental and analytical
tools such as beakers, Petri dishes, flasks, test tubes, centrifugal
tubes, etc.; optical parts for medical treatment such as plastic lenses
for medical test, etc.; piping materials such as transfusion tubes for
medical treatment, pipes, joints, valves, etc.; artificial organs and
parts such as dental plates, artificial hearts, artificial dental roots,
etc.; and the like); materials for treatment of electronic parts (e.g.,
containers for treatment and transportation such as tanks, trays,
carriers, cases, etc.; protecting materials such as carrier tapes,
separation films, etc.; pipings such pipes, tubes, valves, flowmeters,
filters, pumps, etc.; liquid-holding containers such as sampling
containers, bottles, ampoule bags, etc.; and the like); general insulating
materials (e.g., covering materials for electric wires and cables,
insulating materials for electronic instruments for public welfare and
industry, meters, instruments such as copying machines, computers,
printers, televisions, video-cameras etc.), etc.; circuit boards (e.g.,
hard printed circuit boards, flexible printed circuit boards, multilayer
printed circuit boards, etc., particularly high-frequency circuit boards
for satellite communication instruments required for high-frequency
characteristics); materials for transparent and conductive films (e.g.,
liquid crystal substrates, optical memories, flat-surface heaters such as
defrosters for cars and airplanes, etc.), sealing materials for
electro-conductors (e.g., transistors, IC, LSI, LED, etc.) and parts
therefor, sealing materials for electric and electronic parts (e.g.,
motors, condensers, switches, sensors, etc.), structural materials for
parabola antennas, flat antennas and radar domes; and the like.
Working examples;
The present invention will be illustrated specifically with reference to
the following referential examples, examples and comparative examples.
REFERENTIAL EXAMPLE 1
One hundred and fifty parts by weight of dicyclopentadiene was dissolved in
300 parts by weight of cyclohexane, and 1 part by weight of 1-hexene was
added as a molecular weight-regulating agent. To this solution were added
as the component (a) 30 parts by weight of a 0.8% cyclohexane solution of
tungsten hexachloride, as the component (b) 4 parts by weight of a 10%
cyclohexane solution of tetrabutyltin and as the third component 0.8 part
by weight of dibutyl ether. Metathesis ring-opening polymerization was
carried out at 70.degree. C. for 1 hour with stirring to obtain a polymer
solution. The polymerization conversion was 100%, and the weight average
molecular weight of the polymer measured by GPC was 23,300.
Referential Example 2
The polymer solution was obtained in the same manner as in Referential
Example 1 except that 105 parts by weight of dicyclopentadiene and 45
parts by weight of norbornene were used in place of 150 parts by weight of
dicyclopentadiene. The polymerization conversion was 100%, and the weight
average molecular weight of the polymer was 30,500.
Referential Example 3
The polymer solution was obtained in the same manner as in Referential
Example 1 except that tetraphenyltin was used in place of tetrabutyltin.
The polymerization conversion was 100%, and the weight average molecular
weight of the polymer was 23,900.
Referential Example 4
The polymer solution was obtained in the same manner as in Referential
Example 1 except that norbornene was used in place of dicyclopentadiene
and tetramethyltin was used in place of tetrabutyltin. The polymerization
conversion was 100%, and the weight average molecular weight of the
polymer was 27,000.
Referential Example 5
One hundred parts by weight of tetrahydroindene was dissolved in 244 parts
by weight of cyclohexane. To this solution were added as the component (a)
54 parts by weight of a 0.8% cyclohexane solution of tungsten
hexachloride, as the component (b) 1.8 parts by weight of a 23%
cyclohexane solution of ethylaluminum dichloride and as the third
component 0.055 part by weight of ethyl alcohol. Metathesis polymerization
was carried out at 25.degree. C. for 1 hour with stirring to obtain a
polymer solution. The polymerization conversion was 38%, and the weight
average molecular weight of the polymer measured by GPC was 76,200.
Referential Example 6
One hundred parts by weight of 8-methyltetracyclododecene was dissolved in
250 parts by weight of cyclohexane, and 0.5 part by weight of 1-hexene was
added as a molecular weight-regulating agent. To this solution were added
as the component (a) 1.6 parts by weight of titanium tetrachloride, as the
component (b) 11 parts by weight of a 15% cyclohexane solution of
triethylaluminum and as the third component 3.4 parts by weight of
triethylamine. Metathesis ring-opening polymerization was carried out at
40.degree. C. for 1 hour with stirring to obtain a polymer solution. The
polymerization conversion was 85%, and the weight average molecular weight
of the polymer measured by GPC was 34,800.
Example 1
To a 2-liter autoclave equipped with a stirrer were added 100 g of the
polymer solution obtained in Referential Example 1, 0.38 g of cobalt(III)
acetylacetonate as the component (c) and 300 g of cyclohexane. After
replacing the air in the autoclave by hydrogen, a solution of 0.84 g of
triisobutylaluminum, the component (d), in 9.16 g of cyclohexane was added
to the autoclave. Reaction was carried out at 80.degree. C. for 1 hour
under a hydrogen pressure of 10 kg/cm.sup.2. At a point when thirty
minutes elapsed after beginning of the reaction, it was observed that
hydrogen absorption had been completed. The hydrogenation rate of the
polymer was 98.9%.
Example 2
Reaction was carried out in the same manner as in Example 1 except that the
polymer solution obtained in Referential Example 2 was used in place of
the polymer solution obtained in Referential Example 1, and that a
solution of 1.68 g of triisobutylaluminum, the component (d), in 8.32 g of
cyclohexane was used. At a point when thirty minutes elapsed after
beginning of the reaction, it was observed that hydrogen absorption had
been completed. The hydrogenation rate of the polymer was 99.4%.
Example 3
Reaction was carried out in the same manner as in Example 1 except that
1.90 g of cobalt(III) acetylacetonate was used as the component (c), a
solution of 4.20 g of triisobutylaluminum, the component (d), in 5.80 g of
cyclohexane was used, and that the reaction temperature was 60.degree. C.
At a point when thirty minutes elapsed after beginning of the reaction, it
was observed that hydrogen absorption had been completed. The
hydrogenation rate of the polymer was 99.9%.
Example 4
Reaction was carried out in the same manner as in Example 1 except that the
polymer solution obtained in Referential Example 6 was used in place of
the polymer solution obtained in Referential Example 1, 1.90 g of
cobalt(III) acetylacetonate was used as the component (c), a solution of
4.20 g of triisobutylaluminum, the component (d), in 5.80 g of cyclohexane
was used, and that the reaction temperature was 60.degree. C. At a point
when thirty minutes elapsed after beginning of the reaction, it was
observed that hydrogen absorption had been completed. The hydrogenation
rate of the polymer was 99.9%.
Example 5
Reaction was carried out in the same manner as in Example 1 except that
0.14 g of nickel(II) acetylacetonate was used as the component (c), and a
solution of 0.42 g of triisobutylaluminum, the component (d), in 9.58 g of
cyclohexane was used. At a point when thirty minutes elapsed after
beginning of the reaction, it was observed that hydrogen absorption had
been completed. The hydrogenation rate of the polymer was 99.9%.
Example 6
Reaction was carried out in the same manner as in Example 1 except that the
polymer solution obtained in Referential Example 2 was used in place of
the polymer solution obtained in Referential Example 1, 0.14 g of
nickel(II) acetylacetonate was used as the component (c), and that a
solution of 0.42 g of triisobutylaluminum, the component (d), in 9.58 g of
cyclohexane was used. At a point when thirty minutes elapsed after
beginning of the reaction, it was observed that hydrogen absorption had
been completed. The hydrogenation rate of the polymer was 99.9%.
Example 7
Reaction was carried out in the same manner as in Example 1 except that the
polymer solution obtained in Referential Example 5 was used in place of
the polymer solution obtained in Referential Example 1, 0.14 g of
nickel(II) acetylacetonate was used as the component (c), and that a
solution of 0.42 g of triisobutylaluminum, the component (d), in 9.58 g of
cyclohexane was used. At a point when thirty minutes elapsed after
beginning of the reaction, it was observed that hydrogen absorption had
been completed. The hydrogenation rate of the polymer was 99.9%.
Example 8
Reaction was carried out in the same manner as in Example 1 except that the
polymer solution obtained in Referential Example 4 was used in place of
the polymer solution obtained in Referential Example 1, 0.14 g of
nickel(II) acetylacetonate was used as the component (c), and that a
solution of 0.42 g of triisobutylaluminum, the component (d), in 9.58 g of
cyclohexane was used. At a point when thirty minutes elapsed after
beginning of the reaction, it was observed that hydrogen absorption had
been completed. The hydrogenation rate of the polymer was 99.9%.
Example 9
Reaction was carried out in the same manner as in Example 1 except that the
polymer solution obtained in Referential Example 2 was used in place of
the polymer solution obtained in Referential Example 1, 0.25 g of
bis(cyclopentadienyl)titanium dichloride was used as the component (c),
and that a solution of 0.26 g of n-butyllithium, the component (d), in
9.74 g of cyclohexane was used. At a point when thirty minutes elapsed
after beginning of the reaction, it was observed that hydrogen absorption
had been completed. The hydrogenation rate of the polymer was 91.5%.
Example 10
Reaction was carried out in the same manner as in Example 1 except that
0.25 g of bis(cyclopentadienyl)titanium dichloride was used as the
component (c), a solution of 0.26 g of n-butyllithium, the component (d),
in 9.74 g of cyclohexane was used, the reaction temperature was 60.degree.
C., and that the hydrogen pressure was 30 kgf/cm.sup.2. At a point when
thirty minutes elapsed after beginning of the reaction, it was observed
that hydrogen absorption had been completed. The hydrogenation rate of the
polymer was 97.3%.
Example 11
Reaction was carried out in the same manner as in Example 1 except that
1.00 g of bis(cyclopentadienyl)titanium dichloride was used as the
component (c), a solution of 1.83 g of triethylaluminum, the component
(d), in 8.17 g of cyclohexane was used, the reaction temperature was
60.degree. C., and that the hydrogen pressure was 30 kgf/cm.sup.2. At a
point when thirty minutes elapsed after beginning of the reaction, it was
observed that hydrogen absorption had been completed. The hydrogenation
rate of the polymer was 93.8%.
Example 12
Reaction was carried out in the same manner as in Example 1 except that the
polymer solution obtained in Referential Example 6 was used in place of
the polymer solution obtained in Referential Example 1, 1.00 g of
bis(cyclopentadienyl)titanium dichloride was used as the component (c),
and that a solution of 1.02 g of n-butyllithium, the component (d), in
8.98 g of cyclohexane was used. At a point when thirty minutes elapsed
after beginning of the reaction, it was observed that hydrogen absorption
had been completed. The hydrogenation rate of the polymer was 91.7%.
Example 13
Reaction was carried out in the same manner as in Example 1 except that the
polymer solution obtained in Referential Example 2 was used in place of
the polymer solution obtained in Referential Example 1, 0.30 g of
tetraisopropoxy titanate was used as the component (c), and that a
solution of 0.85 g of triisobuytylaluminum, the component (d), in 9.15 g
of cyclohexane was used. At a point when thirty minutes elapsed after
beginning of the reaction, it was observed that hydrogen absorption had
been completed. The hydrogenation rate of the polymer was 97.5%.
Example 14
Reaction was carried out in the same manner as in Example 1 except that the
polymer solution obtained in Referential Example 3 was used in place of
the polymer solution obtained in Referential Example 1, 1.51 g of
tetraisopropoxy titanate was used as the component (c), and that a
solution of 2.43 g of triethylaluminum, the component (d), in 7.57 g of
cyclohexane was used. At a point when thirty minutes elapsed after
beginning of the reaction, it was observed that hydrogen absorption had
been completed. The hydrogenation rate of the polymer was 92.3%.
Example 15
Reaction was carried out in the same manner as in Example 1 except that the
polymer solution obtained in Referential Example 2 was used in place of
the polymer solution obtained in Referential Example 1, 1.51 g of
tetraisopropoxy titanate was used as the component (c), and that a
solution of 1.36 g of n-butyllithium, the component (d), in 8.64 g of
cyclohexane was used. At a point when thirty minutes elapsed after
beginning of the reaction, it was observed that hydrogen absorption had
been completed. The hydrogenation rate of the polymer was 92.7%.
Example 16
Reaction was carried out in the same manner as in Example 1 except that
1.51 g of tetraisopropoxy titanate was used as the component (c), and that
a solution of 2.12 g of triisobutylaluminum, the component (d), in 7.88 g
of cyclohexane was used. At a point when thirty minutes elapsed after
beginning of the reaction, it was observed that hydrogen absorption had
been completed. The hydrogenation rate of the polymer was 95.4%.
Example 17
To a 2-liter autoclave equipped with a stirrer were added 100 g of the
polymer solution obtained in Referential Example 1, 0.3 g of butyl
glycidyl ether, 0.38 g of cobalt(III) acetylacetonate as the component (c)
and 300 g of cyclohexane. After replacing the air in the autoclave by
hydrogen, a solution of 0.84 g of triisobutylaluminum, the component (d),
in 9.16 g of cyclohexane was added to the autoclave. Reaction was carried
out at 80.degree. C. for 1 hour under a hydrogen pressure of 10
kgf/cm.sup.2. At a point when thirty minutes elapsed after beginning of
the reaction, it was observed that hydrogen absorption had been completed.
The hydrogenation rate of the polymer was 98.7%.
Using this autoclave, hydrogenation was repeated ten times in total under
the same conditions. The inner surface of the autoclave was examined, but
corrosion was not observed.
Comparative Example 1
Five hundred grams of the polymer solution obtained in Referential Example
1 was added dropwise to 20 liters of violently stirred isopropanol to
coagulate and precipitate the polymer. The polymer was filtered off and
sufficiently washed with isopropanol. By this treatment, the metathesis
polymerization catalyst was inactivated and removed from the polymer. The
resulting polymer was dried at 60.degree. C. for 3 days under reduced
pressure. Thirty grams of the resulting polymer was dissolved in 370 g of
cyclohexane to obtain a polymer solution.
Reaction was carried out in the same manner as in Example 1 except that the
polymer solution obtained above was used in place of the polymer solution
obtained in Referential Example 1. At a point when thirty minutes elapsed
after beginning of the reaction, it was observed that hydrogen absorption
had been completed. The hydrogenation rate of the polymer was 97.4%. The
hydrogenation rate was higher in Example 1.
Comparative Example 2
Cyclohexane was added to the polymer solution obtained in Referential
Example 1 to adjust the polymer concentration to 10 wt. %. One hundred
grams of this polymer solution and an adsorbent, prepared by impregnating
1.0 g of activated clay with 0.5 g of water, were added to a 200-ml flask,
and the mixture was stirred at room temperature for 2 hours. This treated
solution was centrifuged for 30 minutes at 1500 G to remove the adsorbent
containing adsorbed metathesis polymerization catalyst. Thus, the polymer
solution was obtained.
Reaction was carried out in the same manner as in Example 1 except that the
polymer solution obtained above was used in place of the polymer solution
obtained in Referential Example 1. At a point when thirty minutes elapsed
after beginning of the reaction, it was observed that hydrogen absorption
had been completed. The hydrogenation rate of the polymer was 70.4%. The
hydrogenation rate was higher in Example 1 as compared with Example 1.
Comparative Example 3
Reaction was carried out in the same manner as in Example 1 except that the
polymer solution obtained in Comparative Example 3 was used in place of
the polymer solution obtained in Referential Example 1, 1.90 g of
cobalt(III) acetylacetonate was used as the component (c), a solution of
4.20 g of triisobutylaluminum, the component (d), in 5.80 g of cyclohexane
was used, and that the reaction temperature was 60.degree. C. At a point
when thirty minutes elapsed after beginning of the reaction, it was
observed that hydrogen absorption had been completed. The hydrogenation
rate of the polymer was 99.7%. The hydrogenation rate was higher in
Example 3 as compared with Example 3.
Comparative Example 4
Reaction was carried out in the same manner as in Example 1 except that the
polymer solution obtained in Comparative Example 1 was used in place of
the polymer solution obtained in Referential Example 1, 0.14 g of
nickel(II) acetylacetonate was used as the component (c), and that a
solution of 0.42 g of triisobutylaluminum, the component (d), in 9.58 g of
cyclohexane was used. At a point when thirty minutes elapsed after
beginning of the reaction, it was observed that hydrogen absorption had
been completed. The hydrogenation rate of the polymer was 99.7%. The
hydrogenation rate was higher in Example 5 as compared with Comparative
Example 4.
Comparative Example 5
Hydrogenation was repeated ten times in the same autoclave of Example 1 in
the same manner as in Example 1. The inner surface of the autoclave was
examined to find that minute corrosion was observed near the boundary
between the parts of the inner surface with which the reaction solution
contacted and did not contact.
Referential Example 7
Under a nitrogen atmosphere, 300 parts by weight of cyclohexane, 0.48 part
by weight of 1-hexene and 0.30 part by weight of tetrabutyltin were added
to 10 parts by weight of
6-methyl-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene. While
keeping the resulting mixture at 40.degree. C. with stirring, 90 parts by
weight of
6-methyl-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene and 32.0
parts by weight of a 0.5 wt % cyclohexane solution of tungsten
hexachloride were continuously added thereto over 60 minutes. Thereafter,
reaction was carried out for 1 hour to obtain 424 parts by weight of a
ring-opened polymer solution.
This ring-opened polymer solution was analyzed by gas chromatography, and
it was found that the residual monomer was not detected, and that the
conversion to the polymer was nearly 100%.
Referential Example 8
Under a nitrogen atmosphere, 250 parts by weight of cyclohexane, 0.59 part
by weight of 1-hexene and 0.60 part by weight of tetraoctyltin were added
to 7.0 parts by weight of dicyclopentadiene and 3.0 parts by weight of
6-methyl-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene. While
keeping the resulting mixture at 40.degree. C. with stirring, a mixture of
63 parts by weight of dicyclopentadiene and 27 parts by weight of
6-methyl-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene and 39.0
parts by weight of a 0.5 wt. % cyclohexane solution of tungsten
hexachloride were continuously added thereto over 60 minutes. Thereafter,
reaction was carried out for 1 hour to obtain 382 parts by weight of a
ring-opened polymer solution.
This ring-opened polymer solution was analyzed by gas chromatography, and
it was found that either of the monomers, cyclopentadiene and
6-methyl-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene, was not
detected, and that the conversion to the polymer was nearly 100%.
Example 18
To 100 parts by weight of the ring-opened polymer solution obtained in
Referential Example 7 were added 0.14 part by weight of butyl glycidyl
ether and 0.63 g of a nickel-alumina catalyst (N163A produced by Nikki
Kagaku Co.). The resulting mixture was added to a pressure-proof reactor
made of SUS-316. Hydrogen was introduced into the reactor, and
hydrogenation was carried out at 210.degree. C. for 6 hours under a
hydrogen pressure of 45 kg/cm.sup.2. After finish of the reaction, the
reaction solution was diluted with 65 parts by weight of cyclohexane, and
catalyst residues were removed by filtration. Thus, 158 parts by weight of
a solution containing the hydrogenated product of the ring-opened polymer.
Fifty parts by weight of this solution was poured into 150 parts by weight
of isopropyl alcohol with stirring to coagulate the hydrogenated product
of the ring-opened polymer. This coagulated product was recovered by
filtration, washed with 100 parts by weight of isopropyl alcohol and dried
at 120.degree. C. for 40 hours under 1 Torr or less in a vacuum drier.
Thus, 7.0 parts by weight of the hydrogenated product of the ring-opened
polymer of
6-methyl-l,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene.
This hydrogenated product had a number average molecular weight of 29,000
and a weight average molecular weight of 65,000 as values converted to
polystyrene basis by gel.permeation.chromatography, a hydrogenation rate
of 99.8% or more measured by .sup.1 H-NMR spectrum, and a glass transition
temperature of 151.degree. C. measured by differential scanning
calorimetry.
Twenty-five grams of this hydrogenated product was burnt to ashes. The
ashes were dissolved in sulfuric acid and analyzed by ICP analysis. As a
result, it was found that the amount of the tungsten atom in the
hydrogenated product was 25 ppb (detection limit) or less, that of the tin
atom was 25 ppb (detection limit) or less and that of the nickel atom was
25 ppb (detection limit) or less.
The above hydrogenation was carried out four times in succession. After the
fourth hydrogenation was finished, the inner surface of the pressure-proof
reactor was examined, but abnormalities such as corrosion, etc. were not
observed.
Example 19
To 100 parts by weight of the ring-opened polymer solution obtained in
Referential Example 7 were added 0.14 part by weight of butyl glycidyl
ether and 0.081 part by weight of isopropyl alcohol, and the resulting
mixture was stirred at 50.degree. C. for 4 hours to inactivate the
polymerization catalyst. Thereafter, 0.50 part by weight of a
nickel-alumina catalyst (N163A) was added to the mixture which was then
added to the same pressure-proof reactor as used in Example 1. After
introducing hydrogen into the reactor, hydrogenation was carried out at
210.degree. C. for 6 hours under a hydrogen pressure of 45 kg/cm.sup.2.
After finish of the reaction, the reaction solution was diluted with 65
parts by weight of cyclohexane, and catalyst residues were removed by
filtration. Thus, 159 parts by weight of a solution containing the
hydrogenated product of the ring-opened polymer.
Fifty parts by weight of this solution was coagulated and dried in the same
manner as in Example 1 to obtain 7.1 parts by weight of the hydrogenated
product of the ring-opened polymer of
6-methyl-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene.
The same analyses as in Example 18 were carried out, and it was found that
this hydrogenated product has a number average molecular weight of 29,000
and a weight average molecular weight of 65,000, a hydrogenation rate of
99.8% or more and a glass transition temperature of 151.degree. C.
Further, it was found that the amount of the tungsten atom in the
hydrogenated product was 25 ppb (detection limit) or less, that of the tin
atom was 25 ppb (detection limit) or less and that of the nickel atom was
25 ppb (detection limit) or less.
The above decomposition of the polymerization catalyst and hydrogenation
were carried out four times in succession. After the fourth hydrogenation
was finished, the inner surface of the pressure-proof reactor was
examined, but abnormalities such as corrosion, etc. were not observed.
Example 20
To 100 parts by weight of the ring-opened polymer solution obtained in
Referential Example 8 were added 0.19 part by weight of butyl glycidyl
ether and 0.11 part by weight of isopropyl alcohol to inactivate the
polymerization catalyst in the same manner as in Example 2. Thereafter,
0.57 part by weight of a nickel-alumina catalyst (N163A) was added as the
hydrogenation catalyst to the mixture which was then added to the same
pressure-proof reactor as used in Example 1. After introducing hydrogen
into the reactor, hydrogenation was carried out at 210.degree. C. for 6
hours under a hydrogen pressure of 45 kg/cm.sup.2. After finish of the
reaction, the reaction solution was diluted with 90 parts by weight of
cyclohexane, and catalyst residues were removed by filtration. Thus, 180
parts by weight of a solution containing the hydrogenated product of the
ring-opened polymer.
Fifty parts by weight of this solution was coagulated and dried in the same
manner as in Example 1 to obtain 7.1 parts by weight of the hydrogenated
product of the ring-opened polymer of
6-methyl-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene.
The same analyses as in Example 18 were carried out, and it was found that
this hydrogenated product had a number average molecular weight of 27,000,
a weight average molecular weight of 57,000, a hydrogenation rate of 99.8%
or more and a glass transition temperature of 105.degree. C. Further, it
was found that the amount of the tungsten atom in the hydrogenated product
was 25 ppb (detection limit) or less, that of the tin atom was 25 ppb
(detection limit) or less and that of the nickel atom was 25 ppb
(detection limit) or less.
The same decomposition of the polymerization catalyst and hydrogenation as
described above were carried out four times in succession. After the
fourth hydrogenation was finished, the inner surface of the pressure-proof
reactor was examined, but abnormalities such as corrosion, etc. were not
observed.
Example 21
Inactivation of the polymerization catalyst and hydrogenation were carried
out in the same manner as in Example 19 except that 0.065 part by weight
of propylene oxide was used in place of butyl glycidyl ether. Thus, 155
parts by weight of the solution containing the hydrogenated product of the
ring-opened polymer was obtained.
Fifty parts by weight of this solution was coagulated and dried in the same
manner as in Example 1 to obtain 6.9 parts by weight of the hydrogenated
product of the ring-opened polymer of
6-methyl-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene.
The same analyses as in Example 18 were carried out, and it was found that
this hydrogenated product had a number average molecular weight of 29,000,
a weight average molecular weight of 65,000, a hydrogenation rate of 99.8%
or more and a glass transition temperature of 151.degree. C. Further, it
was found that the amount of the tungsten atom in the hydrogenated product
was 25 ppb (detection limit) or less, that of the tin atom was 25 ppb
(detection limit) or less and that of the nickel atom was 25 ppb
(detection limit) or less.
The same decomposition of the polymerization catalyst and hydrogenation as
described above were carried out four times in succession. After the
fourth hydrogenation was finished, the inner surface of the pressure-proof
reactor was examined, but abnormalities such as corrosion, etc. were not
observed.
Example 22
Inactivation of the polymerization catalyst and hydrogenation were carried
out in the same manner as in Example 19 except that 0.30 part by weight of
powdery zinc was used in place of butyl glycidyl ether. Thus, 158 parts by
weight of the solution containing the hydrogenated product of the
ring-opened polymer was obtained.
Fifty parts by weight of this solution was coagulated and dried in the same
manner as in Example 1 to obtain 7.0 parts by weight of the hydrogenated
product of the ring-opened polymer of
6-methyl-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene.
The same analyses as in Example 18 were carried out, and it was found that
this hydrogenated product had a number average molecular weight of 29,000,
a weight average molecular weight of 65,000, a hydrogenation rate of 99.8%
or more and a glass transition temperature of 151.degree. C. Further, it
was found that the amount of the tungsten atom in the hydrogenated product
was 25 ppb (detection limit) or less, that of the tin atom was 25 ppb
(detection limit) or less, that of the nickel atom was 25 ppb (detection
limit) or less and that of the zinc atom was 25 ppb (detection limit) or
less.
The same decomposition of the polymerization catalyst and hydrogenation as
described above were carried out four times in succession. After the
fourth hydrogenation was finished, the inner surface of the pressure-proof
reactor was examined, but abnormalities such as corrosion, etc. were not
observed.
Comparative Example 6
Hydrogenation was carried out in the same manner as in Example 18 except
that butyl glycidyl ether was not used, to obtain 154 parts by weight of a
solution containing the hydrogenated product of the ring-opened polymer.
Fifty parts by weight of this solution was coagulated and dried in the same
manner as in Example 1 to obtain 7.2 parts by weight of the hydrogenated
product of the ring-opened polymer of
6-methyl-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene.
The same analyses as in Example 18 were carried out, and it was found that
this hydrogenated product had a number average molecular weight of 29,000,
a weight average molecular weight of 65,000 and a glass transition
temperature of 151.degree. C., but that its hydrogenation rate was 98.5%.
Further, it was found that the amount of the tungsten atom in the
hydrogenated product was 25 ppb (detection limit) or less, that of the tin
atom was 25 ppb (detection limit) or less and that of the nickel atom was
25 ppb (detection limit) or less.
The same hydrogenation as described above was carried out four times in
succession. After the fourth hydrogenation was finished, the inner surface
of the pressure-proof reactor was examined. As a result, it was found that
minute corrosion was observed at the upper part of the reactor and near
the boundary between the lower and upper parts of the inner surface with
which the hydrogenation solution contacted and did not contact,
respectively.
According to the method of the present invention, before the beginning of
hydrogenation of the polymer obtained from the monomer, there is no need
to remove the metathesis polymerization catalyst used in the
polymerization of the monomer. Because of this, the hydrogenation can be
carried out with a good efficiency and besides in the absence of the
inactivating agent for the metathesis polymerization catalyst disturbing
the activity of the hydrogenation catalyst. Therefore, the hydrogenation
is easy and provides the hydrogenated product of high hydrogenation rate.
Further, according to the method of the present invention, the inner
surface of a hydrogenation reactor can be prevented from corrosion by a
hydrogen halide, and besides steps for removing the polymerization
catalyst and its residues can be omitted, so that this method is very
advantageous for industrial production.
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